Proton-mediated reversible switching of metastable ferroelectric phases with low operation voltages

The exploration of ferroelectric phase transitions enables an in-depth understanding of ferroelectric switching and promising applications in information storage. However, controllably tuning the dynamics of ferroelectric phase transitions remains challenging owing to inaccessible hidden phases. Here, using protonic gating technology, we create a series of metastable ferroelectric phases and demonstrate their reversible transitions in layered ferroelectric α-In₂Se₃ transistors. By varying the gate bias, protons can be incrementally injected or extracted, achieving controllable tuning of the ferroelectric α-In₂Se₃ protonic dynamics across the channel and obtaining numerous intermediate phases. We unexpectedly discover that the gate tuning of α-In₂Se₃ protonation is volatile and the created phases remain polar. Their origin, revealed by first-principles calculations, is related to the formation of metastable hydrogen-stabilized α-In₂Se₃ phases. Furthermore, our approach enables ultralow gate voltage switching of different phases (below 0.4 volts). This work provides a possible avenue for accessing hidden phases in ferroelectric switching.